JPS60230651A - Preparation of heat developable color photosensitive material - Google Patents

Abstract

PURPOSE:To enhance stability of a coating fluid in preparation and storage, and to improve photographic characteristics by allowing the coating fluid for forming a photosensitive material contg. at least parts of an org. silver salt and a binder, etc., or its intermediate compsn. to stay at a prescribed temp. before using it for coating. CONSTITUTION:The coating fluid or its intermediate compsn. contg. at least parts of an org. silver salt and a binder, of the whole coating fluid for forming a photosensitive material formed on a support and contg. photosensitive silver halide, the org. silver salt, a developing agent, a dye donor, and the binder is allowed to stay at 20-60 deg.C for >=30min after preparing it and before using it, and then, the support is coated with it. The coating compsn. can be stabilized by allowing it to stay in said conditions, though constituents different in solubility product and the binder, etc. retarding the access to equilibrium are presented together in the coating compsn. The rest of said org. silver salt and the binder, and the other constituents may be added immediately before coating. Such a coating fluid is good in stability in its preparation and storage, and the photographic characteristics of the heat developable color photosensitive material thus obtained has also superior stability.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing a heat-developable color photosensitive material, and more specifically, to a method for producing a heat-developable color photosensitive material with improved stability during production and storage. Regarding the manufacturing method.

(Prior Art) A method in which the development step for obtaining a color image is performed by dry heat treatment has many advantages over the conventional wet method in terms of processing time, cost, and concerns about pollution. Therefore, many proposals regarding such heat-developable color photosensitive materials have been made in recent years.
No. 179840, No. 57-186744, No. 57-1
No. 98458, No. 57-207250, No. 58-40
No. 551, No. 58-58543, No. 58-79247
No. 57-122596, Patent Application No. 57-1328
No. 84, No. 57-179236, No. 57-22967
No. 1, No. 57-229674, No. 57-229675
No. 58-33363, No. 58-33364, No. 58-34083, JP-A No. 58-116537, No. 58-123533, No. 58-149046, No. 5
No. 8-14947, etc.

The basic composition of the heat-developable color photosensitive materials according to these proposals consists of a photosensitive element and an image receiving element, and the photosensitive element basically contains an organic silver salt, a photosensitive silver halide, a developer (reducing agent),
It consists of a dye-providing compound and a binder. That is, original information is given to the photosensitive silver halide through image exposure, and during thermal development, dissolution physical development occurs between the organic silver salt and the photosensitive silver halide in accordance with the optical information under the action of a developer. An image-forming dye is released or formed by reacting the developer, which may or may not have acted, with the dye-providing compound. The image-forming dye obtained by thermal development is transferred to an image-receiving element to form an image.

In order to produce such a heat-developable color photosensitive material, basically (a) photosensitive silver halide, (b) organic silver salt, (
C) A developer, (d) a dye-providing compound, and (e) a binder are mixed to form a coating solution, which is coated onto a support and dried, depending on the manufacturing method, but each of the components (a) to (e) above There are two methods for mixing these to form a coating solution: a batch method and a continuous method as described below.

The batch method is a method in which all of the above ingredients are added and mixed in one pot, and then the resulting coating solution is applied to a support, etc. This method allows for quality checks in advance. It has the characteristic that uniform quality can be obtained from the same lot.

On the other hand, the continuous method is a method in which the above-mentioned components are firstly mixed into a pipeline and the coating liquid is applied continuously. It is characterized by being efficient and shortens the time from application to application.

When manufacturing a heat-developable color photosensitive material such as the one according to the present invention, even if the composition of the photosensitive material is the same, depending on the conditions of the manufacturing method, storage of the heat-developable color photosensitive material may be required, regardless of whether it is a batch method or a continuous method. It has been pointed out that there is a drawback that the stability fluctuates significantly.

(Object of the Invention) Therefore, the first object of the present invention is to provide a method for producing a heat-developable color photosensitive material that has excellent stability during production and storage; An object of the present invention is to provide a method for producing a heat-developable color photosensitive material with stable properties.

(Structure of the Invention) The object of the present invention is to provide a coating composition containing at least (a) a photosensitive silver halide, Φ) an organic silver salt, (C) a developer, (d) a dye-providing compound, and (e) a binder. In a method for producing a heat-developable color photosensitive material in which a liquid is coated on a support, after preparing a coating liquid or a coating liquid intermediate composition containing at least a part of the organic silver salt and a binder, This can be achieved by a method for producing a heat-developable color photosensitive material, which is coated on a support after being stagnated at a temperature of 30 minutes or more.

The invention will now be described in more detail.

The method for producing a heat-developable color photosensitive material of the present invention (hereinafter referred to as the "method of the present invention") comprises at least an organic silver salt of each of the above-mentioned components (a) to (e) of the heat-developable color photosensitive material and a small amount of a binder. After preparing a coating liquid or a coating liquid intermediate composition containing a portion of both, the coating liquid is stagnated at 20° C. to 60° C. for 30 minutes or more, and then coated on a support.

The coating solution of the present invention includes at least five components: (a) photosensitive silver halide, (b) organic silver salt, (C) developer, (d) dye-providing compound, and (e) binder. The coating liquid intermediate composition refers to a coating liquid containing all of the above five components, but lacking at least one component.

According to the present invention, instability during production or storage, which depends on the production conditions of the heat-developable color photosensitive material, can be reduced.
It is derived from each component of the above-mentioned photosensitive materials, and specifically, organic silver salts, which have a high solubility product compared to the photosensitive silver halide, which is an essential component, have photosensitive materials with different solubility products. The coating solution is stable during manufacturing because it coexists with silver halide, a developer with reducing properties, and a binder that delays reaching equilibrium. It is believed that it takes time to achieve this, and as a result, stability during manufacturing is hampered.

According to the present invention, after preparing the coating liquid or coating liquid intermediate composition, incubating and stagnation at 20°C to 60°C, preferably 25°C to 50°C for at least 30 minutes, and then coating it on the support. It has been found that the stability of photosensitive materials during production and storage is improved.

That is, the temperature at which the coating liquid or coating liquid intermediate composition of the heat-developable color photosensitive material is kept and stagnates after preparation is 20°C.
If it is below 60°C, it will take a long time to stabilize the coating solution, which is undesirable, and if it is at a high temperature above 60°C, the components of the coating solution may deteriorate or decompose.
This is inconvenient because aggregation and the like are likely to occur.

The relationship between temperature (T) and time (1) in the above heat retention and stagnation can be expressed by the following equation.

t = -+c T (In the formula, a, b, and c each represent a constant) According to the above formula, the relationship between temperature and time during storage and stagnation to maintain the stability of the coating solution is as follows. It will be as described d.

(Temperature) (Time) (a) 20°C to (capital) °C 1 hour to 2 hours (b) 30°C
- Part ℃ 45 minutes - 90 minutes (c) 35℃ - 45℃ 30
The pH of the coating solution during storage and stagnation is usually 3-9, preferably 4-7.

Representative examples of embodiments of the present invention include (a) photosensitive silver halide, (b) organic silver salt, (C) developer, (d)
It is preferable that a coating solution formed by mixing five components, a dye-providing compound and (e) a binder, is kept warm and stagnated at 20° C. to 60° C. for 30 minutes or more, and then coated on a support. However, it is not necessary that all of the above five components be mixed in the coating solution, and the present invention can be applied as long as the coating solution or coating solution intermediate composition contains at least a part of an organic silver salt and a binder. After the above manufacturing conditions, that is, preparation of the coating liquid or violet liquid intermediate composition, 2
By insulating and stagnation at 0°C to 60°C for 30 minutes or more, the stability of the photosensitive material during production and storage can be improved.

In such a case, components other than the organic silver salt and binder, such as photosensitive silver halide, developer, dye-providing compound, or other additives, are added to the coating solution immediately before coating (in-line addition). You can also use it. Specifically, a coating liquid intermediate composition containing at least a part of (b) an organic silver salt and (e) a binder is kept warm and stagnated;
A method of in-line addition of (a) photosensitive silver halide, (C) developer, (d) dye-providing compound, and (f) other additives, at least the above (b) organic silver salt, and (e) binder. The coating liquid intermediate composition containing a part and (d) a dye-providing compound is kept warm and stagnant, and the other components (a),
A method of in-line addition of each component (c) and (f), (b) organic silver salt, (e) at least a portion of the binder (
d) A method in which a coating solution intermediate composition containing a dye-providing compound and (c) a developer is kept warm and stagnant, and other components (a) and (f) are added in-line, (b) an organic silver salt. , (e) at least a portion of the binder, (d) the dye-providing compound, and (a) the coating liquid intermediate composition containing the photosensitive silver halide is insulated and stagnated, and other components (c)
and (f) a method of in-line addition of each component, (b)
) an organic silver salt; (e) at least a portion of the binder; (a)
(a) a method of in-line adding each component of (d) a dye-providing compound and (f) to a coating solution intermediate composition containing a photosensitive silver halide and (c) a developer while keeping it warm and stagnation; Photosensitive silver halide, (b) organic silver salt, (
C) A method in which a coating solution containing a developer, (d) a dye-providing compound, and (e) a binder is kept warm and stagnant, and another component (f) is added in-line, etc., and both embodiments for cholera are included. 〇The coating solution containing each of the above components is kept warm and stagnant for 2 hours before being applied.
The temperature is kept at a temperature of 5°C to 45°C, preferably 30°C to 45°C, and immediately after application, the temperature is kept below 20°C, preferably θ°C to
After being cooled to 15°C, the temperature is 20°C or higher, preferably 6°C to 8°C.
Dry at 0°C.

According to the method of the present invention, it is preferable to gently stir the coating solution or coating solution intermediate composition according to the present invention while it is being kept warm or stagnant.

In the method of the present invention, a pot and a stirring device (e.g. propeller,
Shafts, etc.), valves, etc. are preferably stainless steel surfaces, glass lined, high density, polyethylene treated, Teflon treated, or silicone rubber treated.

In addition, the same considerations as above are required for ultrasonic defoaming equipment, static mixers, filters, pipelines, various detection terminals for packing, etc.

The coating solution consisting of the five components described above is susceptible to problems such as heat retention, deterioration of the photosensitive silver halide, and aggregation of the dye-providing compound.
Since this is undesirable, the application should be completed within the above-mentioned time.

Next, to explain in detail the photosensitive silver halide used in the heat-developable color photosensitive material according to the present invention, the photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, Silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc., grain size is 0.01 μm to 1.0 μm, preferably 0.05 μm to
It is 0.5 μm. The shapes of these silver norogenides include regular tetrahedrons, regular octahedrons, and tetradecahedrons, but those having at least (1,1,1) faces are preferred. Alternatively, the particles may be of a core-shell type in which the internal and external compositions of the particles are different.

The photosensitive silver halide according to the present invention is preferably chemically sensitized using a chemical sensitizer. Chemical sensitizers include sulfur sensitizers, selenium sensitizers, and compounds such as gold, platinum, palladium, etc. These can be used alone or in combination.

Further, the above-mentioned photosensitive silver halide is preferably spectrally sensitized using a sensitizing dye. As these sensitizing dyes, generally well-known dyes such as cyanine dyes and merocyanine dyes can be used. When forming a layer, the photosensitive silver halide according to the present invention can be used with various types of gelatin, including gelatin. It is preferable that it is dispersed in a hydrophilic colloid such as a derivative or a synthetic polymer compound.

As the photosensitive silver halide used in the present invention, the photosensitive silver halide described in the patent specification filed by the present inventors on December 28, 1983 is particularly preferable.

Next, the organic silver salts used in the heat-developable color photosensitive material according to the present invention will be described in detail.
For example, Special Publications No. 43-4924, No. 44-26582, No. 45-18416, No. 45-12700, No. 4
No. 5-22185 and JP-A-49-52626, No. 5
No. 2-31728, No. 52-13731, No. 52-1
No. 41222, No. 53-36224, No. 53-376
No. 10 Each publication 1 Silver salts of aliphatic carboxylic acids such as silver laurate, silver myristate, palmitic acid described in the specifications of U.S. Patent Nos. 3,330,633 and 4,168,980, etc. Silver, silver stearate, silver arachidonate, silver behenate, etc., silver aromatic carboxylates, such as silver benzoate, silver phthalate, etc., and silver salts having an imino group, such as silver benzotriazole, silver saccharin, silver phthalazinone, phthalimide. Silver salts of compounds having a mercapto group or a thione group, such as 2-mercaptobenzoxazole silver, mercapto group silver, 2-mercaptobenzimidazole silver, 3-mercaptophenyl-1.2.4-) lyazole silver, In addition, 4-hydroxy-6-methyl-1゜3.3a,? -tetrazaindene silver, 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene silver, and the like. Also, Research Disclosure (
RD) 16966, 16907, British Patent No. 1
, 590,956 and 1,590,957 can also be used. Among these, silver salts having an imino group, such as silver salts of benzotriazole, are preferred, and silver salts of benzotriazole include, for example, silver benzomeriazole, silver alkyl-substituted benzotriazoles such as silver methylbenzotriazole,
Norogen-substituted benzotriazole silver such as bromobenzotriazole silver, chromium benzotriazole silver, amide substituted benzotriazole silver such as 5-acetamidobenzotriazole silver, and also British Patent No.
, 590,956 and 1.590,9571, such as N-[6-chloro-4-N(3
,5-dichloro-4-hydroxyphenyl)imino-1
-oxo-5-methyl-2,5-cyclohexadiene-
2-ylcu-5-carbamoylbenzotriazole silver salt, 2-benzotriazol-5-ylazo-4-methoxy-1-naphthol silver salt, 1-benzotriazole-5
-ylazo-2-naphthol silver salt, N-benzotriazol-5-yl-4-(4-dimethylaminophenylazo)benzamide silver salt, and the like.

Particularly useful organic silver salts in the present invention are JP-A-58-11
It has a hydrophilic group as shown in No. 8638.

For example, 4-hydroxybenzotriazole silver, 5-hydroxybenzotriazole silver, 4-sulfobenzotriazole silver, 5-sulfobenzotriazole silver, benzotriazole silver-4-sodium sulfonate, benzotriazole silver-sodium 5-sulfonate, benzotriazole silver Silver triazole-4=potassium sulfonate, silver benzotriazole-5-potassium sulfonate, silver benzotriazole-4-ammonium sulfonate, silver benztriazole-5-ammonium sulfonate, silver 4-carboxybenzotriazole, 5-carboxybenzo triazole silver, benzotriazole silver-4-sodium carboxylate,
Sodium benzotriazole silver-5-carboxylate, potassium benzotriazole silver-4-carboxylate, potassium benzotriazole silver-5-carboxylate, ammonium benzotriazole silver-4-carboxylate, ammonium benzotriazole silver-5-carboxylate, 5-Carbamoylbenzotriazole silver, 4-sulfamoylbenzotriazole silver, 5-carboxy-6-hydroxybenzotriazole silver, 5-carboxy 7-sulfobenzotriazole silver, 4-hydroxy-5-sulfobenzotriazole silver, 4- Hydroxy-7-sulfobenzotriazole silver, 5,6-dicarboxybenzotriazole silver, 4,6-dihydroxybenzotriazole silver, 4
-Hydroxy-5-chlorobenzotriazole silver, 4-
Silver hydroxy-5-methylbenzotriazole, silver 4-hydroxy-5-methoxybenzotriazole, silver 4-hydroxy-5-nitrobenzotriazole, silver 4-hydroxy-5-cyanobenzotriazole, silver 4-hydroxy-5-amino Silver benzotriazole, 4-hydroxy-5-acetamidobenzotriazole silver, 4-hydroxy-5-benzenesulfonamidobenzotriazole silver, 4-hydroxy-5-hydroxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-ethoxycarbonylmethoxy Silver benzotriazole, Silver 4-hydroxy-5-carboxymethylbenzotriazole, Silver 4-hydroxy-5-ethoxycarbonylmethylbenzotriazole, Silver 4-hydroxy-5-phenylbenzotriazole, Silver 4-hydroxy-5-(p-nitro phenyl)benzotriazole silver, 4-hydroxy-5
-(p-sulfophenyl)penztriazole silver, 4-
Sulfo-5-chlorobenzotriazole silver, 4-sulfo-5-methylbenzotriazole silver, 4-sulfo-5-
Silver methoxybenzotriazole, Silver 4-sulfo-5-cyanobenzotriazole, Silver 4-sulfo-5-aminobenzotriazole, Silver 4-sulfo-5-acetamidobenzotriazole, Silver 4-sulfo-5-benzenesulfonamidobenzotriazole , 4-sulfo-5-hydroxycarbonylmethoxybenzotriazole silver, 4-sulfo-5-ethoxycarbonylmethoxybenzotriazole silver, 4-hydroxy-5-carboxybenzotriazole silver, 4-sulfo-5-carboxymethylbenzotriazole silver, 4-Sulfo-5-ethoxycarbonylmethylbenzotriazole silver, 4-sulfo-5-phenylbenzotriazole silver, 4-sulfo-5-(p-nitrophenyl) pen/) IJ azole silver, 4-sulfo-
5-(p-sulfophenyl)benzotriazole silver, 4
-Sulfo-5-methoxy-6-chlorobenzotriazole silver, 4-sulfo-5-chloro-6-carboxybenzotriazole silver, 4-carboxy-5-chlorobenzotriazole silver, 4-carboxy-5-methylbenzotriazole silver , 4-carboxy-5-nitrobenzotriazole silver, 4-carboxy-5-aminobenzotriazole silver, 4-carboxy-5-methoxybenzotriazole silver, 4-carboxy-5-acetamidobenzotriazole silver, 4. -carboxy-5-ethoxycarbonylmethoxybenzotriazole silver, 4-carboxy-5
-Carboxymethylbenzotriazole silver, 4-carboxy-5-phenylbenzotriazole silver, 4-carboxy-5-(p-nitrophenyl)penzotriazole silver, 4-carboxy-5-methyl-7-sulfobenzotriazole silver, etc. can be mentioned. These compounds may be used alone or in combination of two or more.

The organic silver salt according to the present invention may be isolated and used by dispersing it in a binder for a photosensitive layer by an appropriate means, or the silver salt may be prepared in a binder for a photosensitive layer,
It may be used as is without isolation. The amount of the organic silver salt used is 1 n? Hit 0051~
10. Or is preferably 0.2t to 5.02t.

Further, examples of the developer used in the heat-developable color photosensitive material of the present invention include, for example, U.S. Pat.
Specifications of each issue, RD-12146, RD-15108
, RD-15127 and JP-A-56-27132, p-phenylenediamine type and p-aminophenol type developing agents, phosphoroamide phenol type and sulfonamide phenol type developing agents, and hydrazone type color developing agents. , Japanese Patent Publication No. 57-18674
No. 4, Patent Application No. 57-122596, No. 57-1606
No. 98, No. 57-126054, No. 58-33363
It can be advantageously used in the case of the heat transferable dye-providing substance described in No. 58-33364. Diffusible dyes are released or formed by oxidative coupling of the developer with these thermally transferable dye-providing materials. Also,
U.S. Patent No. 3,342,599, U.S. Patent No. 3.719,4
No. 92, JP-A-53-135628, JP-A No. 54-790
Color developing agent precursors described in No. 35 and the like can also be advantageously used.

In the present invention, the sulfamino acid type developer described in JP-A-56-146133 is particularly useful.

Other color one-type methods include, for example, JP-A-57-17
No. 9840, No. 57-102487, Patent Application No. 57-2
No. 29648, No. 57-229672, No. 57-22
No. 5928 and the like, it is not necessary to use the above-mentioned developer, and the following developer can be used.

i.e. thiphenols (e.g. p-phenylphenol, p-
-Methoxyphenol, 2,6-di.

tert-butyl-p-cresol, N-methyl-p-
amine phenol, etc.), sulfonamide phenol M (
For example, 4-benzenesulfonamidophenol, 2-
benzenesulfonamidophenol, 2,6-cyclo-4-benzenesulfonamidophenol, 2,6-dipromo-4-(p-toluenesulfonamido)phenol, etc.), or polyhydroxybenzenes (e.g., hydroquinone, tert-butylhydroquinone, .6
-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-calphoquinaphthol, etc.), hydroxybinaphthyls and methylene bisna-7tols (e.g. 1,1'-dihydroxy-2
, nobinaphthyl, 6,6'-dibromo-2゜2'-dihydroxy-1,1'-binaphthyl, 6,6'-dinitro-2,2'-dihydroxy 1,1'-binaphthyl, 4
．． 4'-dimethoxy-1,1'-dihydroxy-2,2
'-binaphthyl, bis(2-hydroxy-1-naphthyl)methane, etc.), methylenebisphenols (e.g. 1,
1-bis(2-hydroxy-3,5-dimethylphenyl)-3,5,5-)dimethylhexane, et al.

l-bis(2-hydroxy-3-tert-butyl-5
-methylphenyl)methane, 1,1-bis(2-nidroxy-3,5-di-tert-phthylphenyl)methane, 2+6-methylenebis(2-hydroxy-3-te
rt-butyl-5-methylphenyl)-4-methylphenol α-phenyl-α9α-bis(2-hydroxy-
3,5-di-tert-butylphenyl)methane, α-
phenyl-α,α-bis(2-hydroxy-3-ter
t-Butyl-5-methylphenyl)methane, '1.1-
Bis(2-hydroxy-a, 5-dimethylphenyl)-2-methylpropane, 1,1.5.5-tetrakis(2-hydroxy-3,5-dimethylphenyl)-2,
4-ethylpenkune, 2゜2-bis(4-hydroxy-
a, 5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3-methyl-5-tert-butylphenyl), propane, 2,2-bis(4-hydroxy-3,5-di-tert- (butylphenyl)furopane, etc.), ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones, and pacific diamines.

These developers can be used alone or in combination of two or more. The amount of the developer to be used depends on the type of organic acid silver salt, the type of photosensitive silver halide, and the types of other additives used, but it is usually 0.00% per mole of the organic acid silver salt. The amount ranges from 0.05 mol to 10 mol, preferably from 0.1 mol to 3 mol.

Examples of dye-providing compounds that can be used in the heat-developable color photosensitive material of the present invention include, for example, JP-A-57-179
No. 840, No. 57-186744, No. 58-1165
No. 37, No. 58-123533, No. 57-14904
6 No. 1, Tokugan Sho, No. 57-122596, No. 57-1
No. 60698, No. 57-205447, No. 57-22
No. 4883, No. 57-224884, No. 57-229
No. 671, No. 57-229647, No. 57-2259
Examples include dye-providing compounds that can be used in diffusion transfer type heat-developable photosensitive materials as described in No. 29, No. 58-33363, No. 58-33364, and No. 58-34083.

The dye-providing compound preferably used in the present invention is of a dye-forming type, and has the following general formula (1) % formula % General formula (1) Cp -X where Cp is a coupler residue excluding an active hydrogen atom. , and Cp is a coupler residue having no hydrophilic group such as a sulfo group or carboxy group or a group containing such a hydrophilic group other than the active position.

X represents a group that can be separated from the coupler during the coupling reaction, and X also has one or more hydrophilic groups such as a sulfo group or hacarboxylic group, or a group containing these hydrophilic groups. , preferably has a straight chain or branched alkyl group having 8 or more carbon atoms.

Examples of the coupler residue represented by Cp include those represented by the following general formulas (If) to (■).

General formula (n) General formula (DI) 7 General formula (IV) Re　C0CHCORt.

General formula (V) General formula (Vl) General formula (■) In the above formula, R1+ R2+ Rs and R4 are each a hydrogen atom, a halogen atom (preferably a chlorine atom, a bromine atom, an iodine atom), an alkyl group (preferably Carbon number 1-24
an alkyl group such as methyl, ethyl, butyl,
Examples include groups such as t-octyl, n-dodecyl, n-pentadecyl, cyclohexyl, etc., but further alkyl groups substituted with an aryl group, such as a phenyl group, may also be a benzyl group or a phenethyl group), Substituted or unsubstituted aryl group (e.g. phenyl group, naphthyl group, tolyl group, mesityl group), acyl group (e.g. acetyl group, tetradecanoyl group, pivaloyl group, substituted or unsubstituted benzoyl group), alkyloxy carbonyl group (e.g. methoxycarbonyl group, benzyloxycarbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group, p-)lyloxycarbonyl group, α-naphthoxycarbonyl group), alkylsulfonyl group (e.g. methylsulfonyl group), Arylsulfonyl group (e.g. phenylsulfonyl group), carbamoyl group (e.g. substituted or unsubstituted alkylcarpamoyl group, methylcarbamoyl group, methylcarbamoyl group, tetradecylcarbamoyl group, N-1l-t2,4-di- t
-phenoxybutyl-carbamoyl group, substituted or unsubstituted phenylcarbamoyl group, specifically 2-dodecyloxyphenylcarbamoyl group, etc.), substituted or unsubstituted acylamino group (e.g. n-butylamide group, laurylamide group, substituted optional β-phenoxyethylamide group, phenoxyacetamide group, substituted or unsubstituted benzamide group, methanesulfonamidoethylamide group, β-methoxyethylamide group), alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms) , e.g. methoxy group, ethoxy group, octadecyloxy group), sulfamoyl group (e.g. methylsulfamoyl group, n-
Represents a dodecylsulfamoyl group, a substituted or unsubstituted phenylsulfamoyl group (specifically a dodecylphenylsulfamoyl group), a sulfonylamino group (e.g. methylsulfonylamino group, tolylsulfonylamine group), or a hydroxyl group, etc. .

Further, R and R2 may be combined with each other to form a saturated or unsaturated 5- to 6-membered ring.

R5 is an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms, such as a methyl group, a butyl group, or a heptadecyl group) or an alkoxy group (preferably an alkoxy group having 1 to 18 carbon atoms, such as a methoxy group or an ethoxy group). , octadecyloxy groups), arylamino groups (e.g. anilino groups, and anilino groups substituted with substituents such as halogen atoms, alkyl groups, amido groups or imido groups), substituted or unsubstituted alkylamide groups (e.g. lauryl Amide,
(optionally substituted phenoxyacetamide, phenoxybutanamide groups), substituted or unsubstituted arylamide groups (for example, benzamide groups, and benzamide groups further substituted with halogen atoms, alkyl groups, alkoxy groups, amide groups, etc.), etc. represent.

Further, R, R, and R8 are hydrogen atoms, halogen atoms (preferably chlorine atoms, bromine atoms, and iodine atoms), alkyl groups (preferably alkyl groups having 1 to 2 carbon atoms, such as methyl groups and ethyl groups). , a substituted or unsubstituted alkylamide group (e.g. laurylamide group), an optionally substituted phenoxyalkylamide group (e.g. alkyl-substituted phenoxyacetamide group), a substituted or unsubstituted arylamide group (e.g. benzoylamide group), etc. represents a group.

Next, shi is an alkyl group, preferably an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, a butyl group, an octyl group), a substituted or unsubstituted aryl group (9VLId phenyl group, tolyl group, methoxyphenyl group), etc. represents.

Furthermore, RIO represents an arylamino group (for example, an anilino group, an anilino group further substituted with a halogen atom, an alkyl group, an alkoxy group, an alkylamido group, an arylamido group, an imido group, etc.).

Also RH, R12, R13, R14, Rlg・and R
lg represents a group having the same meaning as the group represented by R+ and R2 described above.

Typical specific examples of the dye-providing compound represented by general formula (1) include the following compounds.

(2). H (3) H H NHCCHC16H33 1 CHC14H29 OOH The above-mentioned four dye-providing compounds used in the present invention vary depending on the heat-developable photosensitive composition, coating conditions, processing method, etc., but are generally 0.00% per mole of organic silver salt. It is used in a range of 0.1 mol to 10 mol, preferably 0.1 mol to 0.2 mol.

The dye-providing compound used in the present invention is used by being contained in a heat-developable photosensitive layer or other photographic constituent layers. , No. 027, it can be dissolved and contained in a high boiling point solvent. Furthermore, in the above dispersion method, the dye-providing compound can be dissolved and contained in the heat-developable photosensitive layer by using a low boiling point solvent in combination with the high boiling point solvent, if necessary.

Examples of the above-mentioned high boiling point solvent include di-n-butyl phthalate, tricresyl phosphate, di-octyl phthalate, n-nonylphenol, etc., and examples of the low boiling point solvent include methyl acetate, butyl propionate, etc.
Known examples include cyclohexanol and diethylene glycol monoacetate. These solvents may be used alone or in combination, and the dye-donating substance dissolved in the solvent may be anionic surfactants such as alkylbenzenesulfonic acids and alkylnaphthalenesulfonic acids and/or sorbitan. It can be mixed with an aqueous solution containing a hydrophilic binder such as gelatin containing a nonionic surfactant such as a monolauric acid ester, emulsified and dispersed using a colloid mill or an ultrasonic dispersion device, and added to the heat-developable photosensitive layer.

The above-mentioned high boiling point solvent is used in an amount that completely dissolves the dye-providing compound, preferably in a range of 0.05 to 100 parts per part of the dye-providing substance.

A preferable dispersion method other than the above is Fischer dispersion. Fischer dispersion refers to dissolving and dispersing a dye-providing substance having a hydrophilic component and a hydrophobic component in the same molecule in an alkaline aqueous solution. This dissolution and dispersion may be carried out by adding an organic solvent that is compatible with water, by heating or stirring (homogenizer, ultrasonic dispersion, etc.), or by using a surfactant. . As the alkali in the alkaline aqueous solution, an inorganic base or an organic base compatible with water can be used, and after dissolving and dispersing the dye-providing substance, the pH can be adjusted as necessary. In this case, an organic or inorganic acid compatible with water can be used as the pH adjuster. The surfactant as a dispersion aid may be an anionic or nonionic surfactant, but anionic surfactants are preferred.

The above Fischer dispersion is also called Agefer dispersion, and is described in British Patent Nos. 45.5ss and 465.
, No. 823, No. 29,897, etc. can be referred to.

Regarding the binder used in the heat-developable color photosensitive material according to the present invention, a hydrophilic binder is used as the binder, but a hydrophobic binder may also be used in combination. The hydrophilic binder in the present invention refers to one that is soluble in water or a mixed solution of water and an organic solvent (a solvent that is optionally miscible with water). For example, proteins such as gelatin, gelatin derivatives, cellulose derivatives, polysaccharides such as dextran, natural substances such as gum arabic, and useful polymers include poly and nylacetals (preferably with a degree of acetalization below 20, e.g. polyvinyl acetals). Liptyral), polyacrylamide, polyvinylpyrrolidone, ethylcellulose, polyvinyl alcohol (preferably those with a saponification rate of 75% or more), etc., but are not limited to these.

If necessary, two or more types may be used in combination. In particular, it is preferred to use a mixture of gelatin or a gelatin derivative and an organic polymeric substance such as polyvinylpyrrolidone or polyvinyl alcohol. The amount of the binder is 1/10 to 10 parts by weight, preferably 1/4 to 4 parts, based on 1 part (by weight) of the organic silver in each photosensitive layer.

The binder used in each layer (hydrophilic colloid) other than the photosensitive layer of the heat-developable color photosensitive material according to the present invention is not particularly limited, and various binders can be used.
As a suitable binder, any hydrophilic or hydrophobic binder can be used depending on the purpose. For example, natural substances such as gelatin, gelatin derivatives, casein, sodium caseinate, proteins such as alhumin, cellulose derivatives such as ethyl cellulose 0, polysaccharides such as dextran, polysaccharides such as agar, arabic comb, gum tragacanth, etc., polyvinyl alcohol, polyvinyl Synthetic polymers such as pyrrolidone, water-soluble polyvinyl acetal, and latex-like vinyl compounds that increase the dimensional stability of photographic feathers and synthetic polymers such as those described below may also be included. Suitable synthetic polymers include U.S. Pat. No. 3,142,586, U.S. Pat. No. 3,193,386, U.S. Pat.
Examples include those described in the specifications of No. 3,287,289 and No. 3,411゜911.

Useful polymers include water-insoluble polymers based on alkyl acrylates or methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates. Suitable polymeric substances include polyvinyl butyral, polyacrylamide, cellulose acetate butyrate, cellulose acetate propionate, polymethyl methacrylate, polyvinylpyrrolidone, polystyrene, ethyl cellulose, polyvinyl chloride,
Chlorinated rubber polyin butylene, butadiene styrene copolymer, vinyl chloride-vinyl acetate copolymer, vinyl acetate-vinyl chloride-maleic acid copolymer, polyvinyl alcohol, polyvinyl acetate, benzyl cellulose, cellulose acetate, cellulose gulo, hionate, cellulose acetate Phthalates are abundant. Moreover, if necessary, a mixture of multiple types or more may be used.

In addition to the above-mentioned components, various additives may be added to the heat-developable color photosensitive material according to the present invention, if necessary. For example, as a development accelerator, U.S. Patent No. 3,220,846
No. 3,531,285, No. 4,012゜26
No. 0, No. 4,060,420, No. 4,088,4
No. 96, No. 4,207,3921 specifications or RD
-15733, 15734, 15776, etc., organic acids described in Japanese Patent Publication No. 12700/1983, 100 described in US Patent No. 3,667,959, S02. As non-aqueous polar solvent compounds having 80-groups and color tone adjusting agents, for example, JP-A-46-49
No. 28, No. 46-6077, No. 49-5019, No. 49-5020, No. 49-91215, No. 49-1
No. 07727, No. 50-2524, No. 50-6713
No. 2, No. 50-67641, No. 50-114217, No. 52-33722, No. 52-99813, No. 5
No. 3-1020, No. 53-55115, No. 53-76
No. 020, No. 53-125014, No. 54-1565
No. 23, No. 54-156524, No. 54-15652
No. 5, No. 54-156526, No. 55-4060,
Publications such as No. 55-4061 and No. 55-32015, as well as West German Patent Nos. 2,140,406 and 2,1
47,063, 4220.618, U.S. Patent No. 3,080,254, 3,847.612, 3,782,941, 3,994,732,
Phthalazinone, phthalimide, pyrazolone, quinazolinone, N-
Hydroxynaphthalimide, penzoxazine, naphthoxazinedione, 2,3-dihydro-phthalazinedione, 2,3-dihydro-1,3-oxazine-2,4-
Dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, incarbostyryl, sulfonamide, 2H-1,3-benzothiazine-2,4-
(3H) dione, benzotriazine, mercaptotriazole, dimerkabutotetrazapentalene, phthalic acid,
A mixture of one or more of these with an imidazole compound or a mixture of at least one acid or an acid anhydride such as phthalic acid or naphthalic acid and a phthalazine compound; Examples include combinations of phthalazine and maleic acid, itaconic acid, quinolinic acid, and gentisic acid. Patent application 1987
-73215, 3-amino-5-mercapto-1,2,4-) lyazoles, 3-acylamino-5-mercapto-1,
2,4-triazoles are also effective.

Furthermore, as an anti-capri agent, for example,
No. 11113, JP-A-49-90118, JP-A No. 49-1
No. 0724, No. 49-97613, No. 50-1010
No. 19, No. 49-130720, No. 50-12333
No. 1, No. 51-47419, No. 51-57435,
No. 51-78227, No. 51-104338, No. 5
No. 3-19825, No. 53-20923, No. 51-5
No. 0725, No. 51-3223, No. 51-42529
No. 51-81124, No. 54-51821, No. 55-93149, etc., as well as British Patent No. 1,
No. 455,271, U.S. Patent No. 3,885,968;
Same No. 3,700, 4.57, Same No. 4゜137.079
No. 4,138,265, West German Patent No. 2,617
, No. 907, etc., or oxidizing agents (e.g., N/% lognoacetamide, N-halogenosuccinimide, perchloric acid and its salts, inorganic perchlorate, etc.). oxides, persulfates, etc.), or acids and their salts (e.g. sulfinic acid, lithium laurate, rosin, diterpene acid, thiosulfonic acid, etc.), or sulfur-containing compounds (e.g. mercapto compound-releasing compounds, thiouracil, disulfide , simple sulfur, mercapto-1,
2,4-triazole, thiazolinthione, polysulfide compounds, etc.), others, oxazoline, 1,2.
4-) Compounds such as lyazole and phthalimide can be mentioned.

In addition, as a stabilizer, a printout preventive agent that particularly prevents printout after processing may be used at the same time.
Halogenated hydrocarbons described in No. 1, No. 50-120328, No. 53-46020, specifically tetrabromobutane, tribromoethanol, 2-bromo-2
-tolylacetamide, 2-bromo2-)lylsulfonylacetamide, 2-tribromomethylsulfonylbenzothiazole, 2I4-bis(tribromomethyl)-
Examples include 6-methyltriazine.

In the present invention, as the hardening agent for the hydrophilic binder, a usual gelatin hardening agent is preferably used, and for example, the following compounds are used.

Namely, inorganic salts such as chromium alum and chromium acetate; aldehydes such as formalin, glyoxal, and glutaraldehyde; N-methane such as dimethylolurea and methyloldimethylhydantoin; Ketones such as pentanedione; Carbamic acids such as dimethylcarbamoylpyridinium chloride; Sulfonic acid esters such as trimethylenebis(methanesulfonate); Sulfonate rides such as ethylenebis(sulfonyl fluoride); Bis(2-chloroethyl)urea , 2,4-dichloro-6-hydroxy-S-)riazine; mucohalogen acids such as mucochloric acid, mucobromic acid, mucophenoxychloric acid; epoxies such as diglycidyl ether; triethylene melamine, hexane Aziridines such as methylenebis(aziridinylcarboxamide); 1-ethyl-a-(3'-dimethylaminepropyl)carbodiimide hydrochloride; 1,3-bis(acryloyl)urea, divinyl ketone, cyacrylamide, 1° 3,5-)Active olefins such as lyacryloylhexahydro-5-)riazine bis(vinylsulfonyl)ether; corner molecule curing agents having functional groups such as partial esters of polyvinyl alcohol and maleic acid, copolymers of glycidyl acrylate, etc. etc. can be sheep.

Regarding the above curing agent, please refer to Japanese Patent Application Laid-Open No. 51-78788,
No. 53-139689, No. 56-27135, U.S. Patent No. 3,843,372, No. 1,870,354,
No. 2,080,019, No. 2,726,162, No. 2,870,013, No. 2.983,611, No. 2
, No. 992, 109, No. 3,047,394, No. 3,
No. 057,723, No. 3,103,437, No. 3,3
No. 21,313, No. 3,325,287, No. 3,36
No. 2,827, No. 3,543゜292, British Patent No. 67
No. 6.628, No. 825,544, No. 1.270,5
78, German Patent No. 672,153, German Patent No. 1,090°427, Japanese Patent Publication No. 34-7133, German Patent No. 46-1872
No. and Research Disclosure, Vol. 176, p. 26 (1)
(December 1978), etc.

A particularly preferred curing agent is U.S. Pat.
No. 57, No. 4,088,495, No. 4,134,76
No. 5, No. 4゜137.082, No. 4,161,407
No., JP-A-49-116154, JP-A No. 49-11874
No. 6, No. 53-57257, No. 53-666960, No. 58-50535, Special Publication No. 47-24259,
Compounds having at least two or more vinylsulfonyl groups in the molecule, such as those described in No. 49-13563, can be used.

In the heat-developable color photosensitive material according to the present invention, a known thermal solvent may be added in order to adjust the balance of dissolution physical development, color development reaction, and diffusion transfer. Examples of the above heat solvent include urea derivatives, amide derivatives, polyethylene glycols, and polyhydric alcohols.

Polyethylene glycol has a molecular weight of 106~
10,000 is preferred.

Specific examples of urea derivatives include urea, thiourea, 1.3-
Dimethylurea, 1,3-diethylurea, diethyleneurea, 1,3-diimpropylurea, 1,3-diptylurea, 1,1-dimethylurea, 1,3-dimethoxyethylurea, 1,3-dimethylthiourea, ↓.

Examples include 3-dipylthiourea, tetramethylthiourea, phenylurea, tetramethylurea, and tetraethylurea.

Specific examples of amide derivatives include acetamide, propionamide, n-butyramide, 1-butyramide, benzamide, diacetamide, dimethylformamide, acetanilide, ethylacetamide acetate, malonamide, 2-chloropropionamide, 3-chloropropionamide, ntalimide, Succinimide, N, N
-Dimethylacetamide, etc.

1i [Specific examples of 1i alcohols include 1.6-hexanediol, D-xylitol, pentaerythritol, 1.4-cyclohexanediol, 1.2-cyclohexanediol, 42'-dihydroxybenzophenone, 1,5- Examples include bentanediol and 1,8-octanediol.

The content of the thermal solvent in the present invention is 5% to 500%, preferably 10% to 300% of the amount of binder in the photosensitive layer. These thermal solvents may be used alone or in combination of two or more.

Also, Japanese Patent Publication No. 46-5393, Japanese Patent Publication No. 50-54329
A post-treatment may be carried out using a sulfur-containing compound as described in each publication.

Furthermore, U.S. Patent No. 3,301,678;
No. 506.444, No. 3,824,103, No. 3
, 844,788, and U.S. Pat. No. 3,6
No. 69,670, No. 4,012,260, No. 4,
It may also contain activator stabilizer precursors and the like described in 060,420 and the like.

In addition to the above-mentioned components, the heat-developable color light-sensitive material of the present invention may further contain a spectral sensitizing agent, )/ration-preventing dye, a fluorescent sensitizer, a hardening agent, an antistatic agent, a plasticizer, and a spreading agent. Various cooling agents, coating aids, etc. may be added.

The heat-developable color photosensitive layer of Hamura according to the present invention is
Basically, it is composed of three layers that are sensitive to blue light, green light, and red light, namely, a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer. When these layers are thermally developed, they release and form dyes that correspond to the three primary colors of yellow, magenta, and cyan, respectively.

The released and formed dyes are basically yellow in the blue-sensitive layer, magenta in the green-sensitive layer, and cyan in the red-sensitive layer, but the combinations are not necessarily limited to the above combinations.

Furthermore, each color-sensitive layer described above may be further divided into two layers with different sensitivities, such as a high-sensitivity layer and a low-sensitivity layer, and may be coated in two layers, or may be further divided into two or more layers and coated in a multilayer manner. It's okay.

In addition to the photosensitive layer, the heat-developable color photosensitive element according to the present invention may be provided with various photographic constituent layers such as an overcoat layer, an undercoat layer (undercoat layer), a backing layer, an intermediate layer, or a filter layer, depending on the purpose. I can do it.

The heat-developable photosensitive layer and other photographic constituent layers according to the present invention can be coated on a wide variety of supports. Supports used in the present invention include plastic films such as cellulose nitrate film ζ cellulose ester film, polyvinyl acetal film, polyamide film, polyethylene film, polyethylene terephthalate film, polycarbonate film A/mu, metals such as aluminum, and glass. Furthermore, paper, baryta paper, synthetic paper, etc. can also be used.

Also, among these supports, those with a small thermal expansion/contraction rate are preferred.

The heat-developable color photosensitive material of the present invention forms a color image on an image-receiving element by imagewise exposure, development by heat treatment, and thermal transfer to an image-receiving element in a stacked relationship with the photosensitive material.

The above-mentioned image receiving element basically only needs to have the function of stopping the transfer of the imagewise distribution of the thermally transferred dye and fixing it.

For example, it may simply be a layer of gelatin or other synthetic polymer, or it may be a layer of aqueous valve or other synthetic pulp fibers. Also, various mordants may be used. The image-receiving element may also include the image-receiving element on a suitable support, and the support may also serve as the image-receiving element. Furthermore, the image receiving layer (element)
may be formed on the same support as the support of the photosensitive element described above.

Further, after the dye image is transferred to the image-receiving element, the image-receiving element may be peeled off, or it may be integrated with the photosensitive layer. Additionally, an opacifying layer (reflective layer) may be included if desired, such layer being capable of reflecting the desired degree of radiation, such as visible light, that may be used to observe the dye image in the receiver element. It is used. The opacifying layer can contain various agents that provide the necessary reflection, such as titanium dioxide.

Effective image-receiving elements (which may have a separate support or may also serve as a support) include synthetic polymer films such as polyethylene terephthalate film, polycarbonate film, polyvinyl chloride film, and polyvinylidene chloride film. , ethyl cellulose film, papers, e.g. evaporator paper, art paper, ipoly paper,
There is also plain paper.

Preferred image-receiving elements for use in the present invention include those having a synthetic polymer layer on a support, such as a baryta support with a polyvinyl chloride layer or a polycarbonate layer, and a polyethylene terephthalate film support with a polyvinyl chloride layer or a polycarbonate layer. Some have a polyvinyl chloride layer or a polycarbonate layer.

Regarding the above, please refer to Japanese Patent Application No. 58-97907 and 58-97907.
No. 128600.

In addition to the above, polyvinyl chloride containing polyalkylene carbonate disclosed in JP-A-53-246, polyvinyl chloride containing silicone oil as disclosed in JP-A-51-88543 and JP-A-52-40557. Furthermore, polyvinyl chloride in which the plasticizer is retained by plasma treatment can also be used as the image-receiving layer according to the present invention.

Various exposure means can be used for the heat-developable color photosensitive material according to the present invention. The latent image is obtained by imagewise exposure to radiation, including visible light. Light sources commonly used for conventional color printing, such as tungsten lamps, mercury vapor lamps, xenon lamps, laser beams, CRTs and LEDs.
A light beam or the like can be used as a light source.

The original drawing may be a line image such as a technical drawing or a photographic image with gradation. Also, printing from the original drawing may be done by contact printing.

In addition, images projected by video cameras and image information sent from television stations are sent directly to CRTs and OFTs.
This image can also be formed and printed on a heat-developable photosensitive material by contact or with a lens.

Furthermore, LEDs (light emitting diodes), which have recently seen great progress, are being used as exposure means and display means in various devices. It is difficult to make an LED that effectively emits blue light. In this case, to reproduce a color image, the LEDs should be designed to emit green, red, and infrared light, and the layers sensitive to these lights should provide yellow, magenta, and cyan pigments, respectively. Bye. That is, the green-sensitive layer may contain a yellow dye-providing compound, the red-sensitive layer may contain a magenta dye-providing compound, and the infrared-sensitive layer may contain a cyan dye-providing compound.

In addition to the above method of directly attaching or projecting the original image, the original image illuminated by a light source can be read by a light-receiving element such as a phototube or COD, or put into the memory of a computer, etc.
After applying so-called image processing to process this information as necessary, this image information is reproduced on a CRT and used as an image-like light source.Based on the processed information, three types of LEDs are directly activated. There is also a method of emitting light for exposure.

Thermal transfer from the heat-developable color light-sensitive material according to the present invention to the thermal transfer image-receiving layer (element) is performed when the heat-developable color light-sensitive material is thermally developed, or when it is reheated after heat development is completed. For heating the thermal transfer chamber, all methods applicable to ordinary heat-developable photosensitive materials can be used. For example, the film may be brought into contact with a heated block or plate, brought into contact with a heated roller or drum, passed through a high-temperature atmosphere, or subjected to high-frequency heating. It is also possible to provide a conductive layer in the heat-developable color photosensitive material or in the image-receiving layer (element) for thermal transfer, and utilize Joule heat generated by electricity or a strong magnetic field. There are no particular restrictions on the heating pattern, including methods of preheating and then reheating.
Continuous rise at high temperature for a short time or low temperature for a long time,
Although descending or recombining or even discontinuous heating is possible, a simple pattern is preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used. Usually, the heating temperature during transfer is 80°C to 200°C, preferably 100°C to
The heating time is usually 1 second to 5 minutes, preferably 5 seconds to 3 minutes.

Thermal transfer using the heat-developable color photosensitive material according to the present invention is as follows:
It is easy to use a commercially available heat developing machine. For example,
1 Image Forming Model 4634” (Sony Tektronix L”y Iberotuber Module 277” (3
Company M), 1 video hard copy unit NWZ-301
” (Japan Radio Co., Ltd.) can be easily applied.

Examples of the present invention are shown below, and embodiments of the present invention include:
It is not limited to these.

Example 1 The following components of a coating solution for a heat-developable color photosensitive material were prepared.

(a) Photosensitive silver iodobromide (93 mol of silver bromide, 7 mol % of silver iodide) with an average grain size of 0.125 μm of photosensitive silver halide, the following optical sensitizing dye and 1.3 4-hydroxy-6-methyl .3a, 7~ Add tetrazaindene stabilizer and further perform sulfur sensitization treatment using sodium thiosulfate to obtain silver halide (in terms of silver) 3
81 F and gelate 7190 t/5000 tnl
A photosensitive silver halide emulsion having a composition containing the following was prepared.

1. Dissolve 4.2f of Schiff-ζ゛thorium and stir. , 5 N
-'=S silver nitrate aqueous solution 20- was added and the pH was adjusted to 6?
-28 Nishinari, -・・2. I then added water to make 400 grams. ′~Pa-Daddy''・-
1 (e) Developer - Poly(4-pininoσ pyrrolytanediol 80f1) Add the following development accelerator 0.7!M and the following developer 202, and after dissolving, adjust the pH to 7.0 and add water. was added to make it 330rnt.

(Development accelerator) CH2-CH,=CH2 (Developer) *, n : e** dissolve,
Alkanol XC (manufactured by DuPont) 5% aqueous solution 140-
An oil-in-water dispersion (dye-donating compound) (1 CM C14) (29 oon (e)) was mixed with 1180 m of a 3.6% gelatin aqueous solution containing Gelatin was divided into each of the components (a) to (a) and added.

(f) Other additives Reaction product of vinyl sulfone hardener (compound below) and taurine sodium salt (molar ratio: 1:o,s)
was dissolved in a solution having a composition of water:ethanol = 1:1 (volume x).

(Hardening agent) C(CH2OCH25O2CH=CH2)4 The following coating solution was mixed and prepared using each of the above components.

(a) Photosensitive silver halide 142-Cb) Organic silver salt 400- (c> Developer 330g) (d) Dye-donor compound 700 tnl.

After mixing each component (a) to (d), the pH was adjusted to 5.50 using a citric acid aqueous solution and a sodium hydroxide aqueous solution while keeping the temperature at 1℃ at 35'C, and the sample was sequentially placed on a support according to the sampling method shown in the table below. was applied. However, a small amount of the above hardener solution (f) was added immediately before coating.

Sampling according to the above Table 1 was carried out at a time of 90 fnl.

After the coating solution was applied and dried, each sample was exposed to 1,600 CMS through a step wedge.

The exposed sample was superimposed on a photographic baryta paper with a polyvinyl chloride layer of 8 to 10 μm thick, and then the sample was placed on top of the photographic baryta paper with a polyvinyl chloride layer of 8 to 10 μm thick.
Heat development was performed at 40° C. for 1 minute to obtain a dye image on receiver paper.

The minimum density, maximum density and relative sensitivity of the dye image for each sample are shown in Table 2 below.

Table 2 From the results shown in the above table, the samples according to the present invention, in which the dwell time before application of the coating solution was 30 minutes or more, were significantly more stable in photographic properties, especially in terms of maximum density and sensitivity, than the comparative samples. I realized that I could be made into a person.

Example 2 The amount of organic silver salt (b) used in Example 1 was changed to 26 f.
A coated sample was prepared in the same manner as in Example 1, except that 1,5-bentanediol in (c) was replaced with 1,6-hexanediol, and the stagnation temperature was changed to 40°C. Sample parts 6 to 10 were obtained.

After the obtained sample was left in an atmosphere of 40° C. and 60% relative humidity for 3 days: it was exposed to light and thermally developed, and a forced deterioration test was also conducted. The results obtained are shown in Table 3 below.

Table 3 From the results in the above table, it can be seen that the samples obtained by the method of the present invention showed no decrease in maximum density compared to the comparative samples, not only in normal tests but also in forced deterioration tests, and that the photographic properties were stabilized. I understand.

Example 3 Each component used in Example 2 was adjusted to pH 5,
5, and heat retention, stagnation, in-line addition, and coating were performed according to the following methods.

Method-1゜Φ) Organic silver salt and (d) dye-providing compound are mixed and heated at 35°C.
After incubation and stagnation for one hour, (a) photosensitive silver halide, (C) developer, and (f) hardener as other additives are added in-line and coated.

Method-2゜a) Organic silver salt, (d) dye-providing compound, and (C) developer are mixed, and after stagnation at 35°C for 1 hour, (a) photosensitive silver halide, (f) other additions are carried out. A hardening agent was added in-line and applied.

Method-3゜ (a) Photosensitive silver halide, (b) organic silver salt, and (d) dye-providing compound are mixed, kept at a temperature of 1 hour, and after stagnation, (C) developer, (f) A hardener as another additive was added in-line and coated.

Method-4゜(b) Organic silver salt was kept warm at ℃ for 1 hour and after stagnation, (a
) A photosensitive silver halide, (C) a developer, (6) a dye-providing compound, and (f) a hardener as other additives are added in-line and coated.

Method-5゜(a) Photosensitive silver halide, (d) dye-providing compound are mixed, kept at 35°C for 1 hour, and after stagnation, (b) organic silver salt, (C) developer, (f) A hardener as another additive was added in-line 7 and coated.

Method - 6゜ (a) Photosensitive silver halide, (C) developer, (d) dye-providing compound are mixed, kept at 35°C for 1 hour, and after stagnation, 6) organic silver salt, (f) others A hardener as an additive was added in-line and coated.

Method-7° Mix (c) developer, (d) dye-providing compound, and heat at 36°C.
After being kept warm for 1 hour and allowed to stagnate, (a) photosensitive silver halide, (b) an organic silver salt, and (f) a hardening agent as other additives were added in-line and coated.

However, in the above case, the temperature was kept within the range of 10°C or higher and lower than 20°C if the temperature did not stagnate.

Sample Nα prepared by method-1 to method-7 above
For Nos. 11 to 17, exposure and thermal development were carried out in exactly the same manner as in Example 1, and the standard deviation rn-1 (n=6) of the relative sensitivity values of the obtained dye images was shown in Table 4 below. From Table 4, it can be seen that the samples prepared by the method of the present invention have significantly more stable sensitivity characteristics than the samples prepared by the method other than the present invention.

(Effect of the invention) After preparing a coating liquid or a coating liquid intermediate composition containing at least a part of an organic silver salt and a binder, the coating liquid or coating liquid intermediate composition is heated at 20°C to 60°C.
The heat-developable color photosensitive material obtained by coating after stagnation for 30 minutes or more has excellent stability in photographic properties.

Procedural Amendment May 29, 1985 Manabu Shiga, Commissioner of the Patent Office1, Indication of the Case, Patent Application No. 86658, filed in 19882, Name of the Invention, Process for Producing Heat-Developable Color Photosensitive Materials, 3o Amendment Person Case and Relationship between patent applicant 〒191 5, "Detailed Description of the Invention" column 6 of the specification subject to amendment, content of amendment 1) The text "High density, polyethylene treatment," on page 14 of the specification tJSXO. 2) On page 10, item 15, line 16, [Teflon treatment, silicone rubber treatment] was corrected to read, “Teflon coating treatment, silicone rubber coating treatment.” 3) On page 35, line 6, the phrase “used in the present invention” should be replaced with “also the following dye-providing substances (13), (+4), (15)”
It is also possible to use a polymeric dye-providing compound obtained by adding a polymerizable group to the molecule and polymerizing it alone or with other copolymerization components, such as in the following.

1.11. ,' (+3) (14) (15) 00 C1l zcI'l 2C11COO11 Used in the present invention'', 4) The same tIS page 57, lines 13, 19, and 5
On page 9, line 9, "poly(4-vinylpyrrolidone)" should be corrected to "poly(N-vinylpyrrolidone)".

Claims (1)

[Claims] At least (a) photosensitive silver halide, (b) organic silver salt,
(C) a developer, (d) a dye-providing compound, and (e) a binder in a method for producing a heat-developable color photosensitive material, which comprises coating a coating solution containing at least the organic silver salt and the binder on a support; A method for producing a heat-developable color photosensitive material, which comprises preparing a coating solution or coating solution intermediate composition containing a portion of the coating solution, allowing it to stagnate at 20°C to 60°C for 30 minutes or more, and then coating it on a support. .